Tetrahedral Connection of ε‑Keggin-type Polyoxometalates To Form an All-Inorganic Octahedral Molecular Sieve with an Intrinsic 3D Pore System

A new type of polyoxometalate-based porous material was successfully synthesized. The new material is the first fully inorganic Keggin-type polyoxometalate-based microporous material with intrinsically ordered open micropores and is the third member of the small family of octahedral molecular sieves (OMSs). Twelve MoO6 or VO6 octahedra surround a central VO4 tetrahedron to form ε-Keggin polyoxometalate building blocks (ε-VMo9.4V2.6O40) that are linked by BiIII ions to form crystalline Mo–V–Bi oxide with a diamondoid topology. The presence of a tetrahedral shape of the ε-Keggin polyoxometalate building block results in arrangement of microporosity in a tetrahedral fashion which is new in OMSs. Owing to its microporosity, this Mo–V–Bi oxide shows zeolitic-like properties such as ion-exchange and molecule adsorption.